Disulfonic acid amides of the anthraquinone series



r r 2,852,535 Ice Patented Sp 1958 DISULFONIC ACID AMIDES OF THE ANTHRAQUINONE SERIES Albin Peter, Binningen, andErhard Wydler, Basel, Switzerland, assignors to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing. Application March 8, 1957 Serial No. 644,739

Claims priority, application Switzerland April 7, 1956 7 Claims. 01. 260-374) The present invention relates to a process for the production of disulfonic acid amides of the anthraquinone series which have the general formula t -Ca 502R t Nags.

x stands for hydrogen, lower alkyl or lower alkoxy,

y for chlorine or bromine,

z for hydrogen or chlorine, when y represents chlorine,

or for hydrogen, when y represents bromine, and

R denotes the radical of a primary or secondary aliphatic amine which possesses at least 3 carbon atoms and may contain further substituents or the radical of a primary, wholly or partially hydrogenated monoor dinuclear aromatic amine, or the radical of morpholine.

wherein I NH- O Nag. (II) wherein x, y and z have the above-mentioned meanings, with 2 mols of a primary or secondary aliphatic amine which contains at least 3 carbon atoms and may carry further substituents, or of a primary, wholly or partially hydrogenated, monoor dinuclear aromatic amine, or of morpholine.

As examples of the starting materials used to prepare the disulfonic acid amides may be mentioned the disulfonic acid chlorides of the derivatives of 1.4-diphenylaminoanthraquinone, 1.4-di-(4'-methyl or ethyl or butyl)- phenylaminoanthraquinone and l.4-di-(4-methoxy or ethoxy)'-phenylaminoanthraquinone, the said chlorides being halogenated in the 6 and/ or 7 positions. One method of preparing the disulfonic acid chlorides is to allow chlorosulfonic acid to act upon the appropriate 1.4-diarylaminoanthraquinone derivatives, which may be sulfonated in the arylamino radicals, until the compounds are soluble in a hot dilute solution of alkalimetal hydroxide but insoluble in water. I

Examples of suitable amines are the primary butyl, amyl, hexyl, cyclohexyl, methylcyclohexyl, octyl and dodecyl amines and their alkoxy derivatives, the diethyl and dibutyl amines, and morpholine. Particularly interesting are cyclohexylamine, n-octylamine, 2-ethylhexylamine, l.1.3.3-tetramethylbutylamine, and 1-amino-5.6.7.8-tetrahydronaphthalene. I

Condensation is accomplished by mixing the disulfonic acid chlorides, in the form of hydrous filter cakes, with the amines. The amines themselves may serve as solvents and diluents; alternatively, water, alcohols such as methyl, ethyl and propyl alcohols, ketones such as acetone, methyl ethyl ketone, ether alcohols such as 2 methoxyand 2- ethoxy-ethanol, dioxane, and mixtures of aqueous alcohols, ketones and ethers can be used. Condensation may be carried out at normal or moderately high temperatures,

e. g. at 20-l00 C., though 35 to 60 C. is the preferred temperature range.

The liberated hydrochloric acid is combined by an excess of the amine employed in condensation or by an acidbinding agent. Suitable acid-binding agents are alkali metal bicarbonates such as sodium and potassium bicarbonate, alkali metal and alkaline earth metal carbonates such as the carbonates of sodium, potassium, lithium, magnesium and calcium, hydroxides of the alkali and alkaline earth metals such as sodium, potassium and calcium hydroxide, magnesium oxide, trisodium phosphate, or a mixture of an alkali metal acetate and one of the previously named acid-binding agents.

The disulfonic acid amides are separated from the reaction mixture by diluting with water, salt water, or dilute hydrochloric or sulfuric acid, and are subsequently filtered ofi. Alternatively, when condensation is eflected in an excess of the amine, the reaction mixture can be evaporated to dryness with reduced pressure and the residue digested with dilute hydrochloric or sulfuric acid and then filtered off.

The condensation products are the disulfonic acid amides corresponding to the disulfonic acid chlorides used as starting materials. The secondary amines are basic enough to initiate condensation before a hydrolysis of the disulfonic acid chlorides occurs. When the suction-filtered disulfonic acid amides of the primary or secondary amines are washed with water, minute quantities of soluble products are removed.

The new disulfonic acid amides of the anthraquinone I series are employed 'for the solution dyeing of fibers which are spun from organic solvents, for printing fabrics of Dacron, Dynel (registered trademarks) and cellulose triacetate, and for pigmenting lacquers, plastics and wood stains.

The following examples illustrate the invention. The parts and percentages specified therein are by weight and the temperatures are in degrees centigrade.

EXAMPLE 1 The humid disulfonic acid chloride of 122 parts of 1.4-di-(4'-methyl)-phenylamino 6.7 dichloroanthraquinone is stirred into a mixture of 105 parts of cyclehexylamine, 54 parts of sodium bicarbonate, 2 parts of a non-ionic wetting agent and parts of water. After 10 hours continuous agitation at 45 the amidation product is isolated by filtration, washed thoroughly With hot water and dried. It is obtained as a green powder which has very good solubility in acetone.

100 parts of cellulose acetate with a content of 54-55% of -splittable acetic acid are mixed with 300 parts of a solvent (e. g. a mixture of 275 parts of acetone and 25 parts of methanol). The mass is stirred and 'left overnight to swell.

On the following day 1 part of the disulfonic acid amide of the anthraquinone series obtained according to the present example are dissolved in 60 parts of the same solvent. This solution is added to the cellulose acetate solution and the whole stirred long enough for 60 parts of the solvent to evaporate.

After being filtered through cotton filters and cotton pressure filters the dyed solution is spun into filament in the same way as undyed cellulose acetate.

EXAMPLE 2 Into a well stirred mixture of 204 parts of cyclohexylamine, 132 parts of anhydrous sodium carbonate, 1 part of a non-ionic wetting agent and 200 parts of water at 55 are entered 1800 parts of the moist paste of the disulfonic acid chloride prepared with 226 parts of 1.4-di- (4-methyl)-phenylamino-6 chloroanthraquinone. The mixture is maintained at 55 for 6 hours. The condensation product is isolated in the manner described in Example 1 and the dyestuff is obtained as a green powder.

When the 132 parts of anhydrous sodium carbonate are replaced by a mixture of 345 parts of crystallized trisodium phosphate and 71 parts of anhydrous disodinm phosphate and the volume of water increased to 1000' parts, equally good results are obtained.

EXAMPLE 3 507 parts of 1.4-di-(4'-methyl)-phenylamino-6-bromoanthraquinone are converted into the disulfonic acid chloride. The reaction product, isolated as a moist filter cake, is stirred into a mixture of 410 parts of cyclohexylamine, 1100 parts of a 30% sodium hydroxide solution, '5 parts of a non-ionic wetting agent and 2600 parts of water at 30. The reaction is allowed to proceed for 12 hours at constant temperature, after which the precipitated disulfonic acid amide is filtered oif and dried. It is a green dyestufi powder soluble in acetone.

EXAMPLE 4 The moist disulfonic acid chloride of Example 1 is stirred into a mixture of 300 parts of cyclohexylamine and 150 parts of isopropyl alcohol. The mass is maintained at 50 for 6 hours, then the reaction mixture is run slowly into a well stirred mixture of 450 parts of concentrated hydrochloric acid, 1200 parts of water and 650 parts of finely crushed ice. The reaction product is suctioned off and washed with water till the filtrate reacts neutral. The filter cake is added to a solution of 5 parts of sodium carbonate in 500 parts of water. After stirring for 30 minutes at EEO-85 the insoluble dyestufif is suctioned oif, washed with hot water till the filtrate reacts neutral, and dried. The resultant dyestuff is identical with that of Example 1.

A nitrocellulose lacquer is prepared by dissolving a mixture of 100 parts of collodion cotton of medium viscosity and 250 parts of an alkyd resin, plasticized with 25 parts of dioctyl phthalate, in 1000 parts of a solvent composed of 225 parts of ethyl glycol acetate, 190 parts of ethyl alcohol, 75 parts of methyl alcohol, 75 parts of methyl acetate, parts of butyl alcohol and 420 parts of ethyl acetate.

5 parts of the disulfonic acid amide obtainable according to the present example are gradually added to 1000 parts of this nitrocellulose lacquer and the mass stirred till the dyestutf has completely dissolved.

A lacquer of blue-green tone is obtained which is suitable for application to the most varied objects.

EXAMPLE 5 The disulfonic acid chloride of Example 3 is stirred'into a suspension of 80 parts of magnesium oxide, 350 parts of sodium acetate, 533 parts of 2-ethylhexylamine and 4000 parts of a 25% aqueous alcohol. The mass is main- .4 tained at 35 for 16 hours. After this time it is weakly acidified with hydrochloric acid and the precipitated dyestuif filtered off, washed thoroughly with water, and dried. The dyestufi? is a green powder which dissolves very well in acetone.

parts of the dyestuff obtained according to this example are stirred into 280 parts of cold water and, after the addition of 150 parts of a mixture of equal quantities of ethyl alcohol and phenol, are brought into solution by heating to 30-40". The mixture is then given 500 parts of a solution of 167 parts of crystal gum in 333 parts of water, followed by 50 parts of thi'oure'a.

The paste thus obtained is eminently suitable for printing on fabrics of Dacron, Dynel (registered trademarks) and cellulose triacetate. After printing the fabric is steamed for 30 minutes without excess pressure, washed with a solution of 1 g. of a sulfonated fatty alcohol per liter water, rinsed and dried. An attractive green print is obtained.

In the following table further disulfonic tacid amides of the anthraquinone series are enumerated which are obtainable according to the particulars of Examples 1 to 5. They are characterized by the disulfom'c acid chloride, the amine employed for condensation, and by the color of the disulfonic acid amide when dissolved in acetone.

Table Example Colorin N o. Disulfonic Acid Chloride of Amine Acetone -Solution 6 l.4-Di-(4-methoxy)-phenyln-Octylamine green.

amino-6.7-diehloroanthraquinone.

7 1.4-Di-'(4-methoxy)-pheny1- technical vDo.

amino-G-ohloroanthraqui- Dodecylamine. none. 8 o Morpholhie Do. 9 lA-Di-(4-eth0xy)-phenyl- Diisobutylamine -Do.

amino-6-chloroanthraquinone. 10 1.4-Dtphenylarnino-6- Diethylaminenn, blue-green.

chloroanthraquinone. 11 1.4-Diphenylamiuo-fi.7-ditechnical green. chloro-anthraquinone. Amylarnine. 12 -.do 3-(Isopropoxy)- Do.

propylamine. 13 1.4-Di-(4' -n1ethy1)-phenyln-Butylamine bluish amino-fi-chloroanthraquigreen. 40 none.

14 1;4-Di-(4-tert.butyl)-phenyl- Cyclohexylamina. green.

amino-fi-chloroanthraquinone. 15 1.4-Di-(4-methyl) -pheny1- 4-Methylcyelo- Do. amino-6.7-dichloroanthrahexylamine. quinone.

d n-Hexy1amine-. Do. n-Octylamine D0. 18 --do Di-n-butylamine yellowish green. 19 .-do 1-Amin0-5.6.7.8- green.

tetrahydronaphthalene. 20 --do Z-Ethylhexyl- Do. amine.

21 -.do 1.1.8.3-Tetra- Do.

methylbutylamine.

Formulae of representative dyestuffs of the foregoing examples are:

EXAMPLES 1 AND 4 BOr-NH-@ u SOFNH 0 N 2,852,535 g a a s EXAMPLE, 2 a a EXAMPLE 21 0 NEG-0H: H: H:

: g O1 SOz-N E-@ G I OH; on. -O SOz-NH-(l-CHr-C-4JH:

NHGCH: (in. an,

EXAMPLE 3 Having thus disclosed the invention what is claimed is: SOTY'NH 1. A disulfonic acid amide of the anthraquinone series 0 NH OH which corresponds to the formula Br A(NHArylSO --R) wherein A stands for an anthraquinone radical which bears the (NH-Aryl-SO R) groups in the positions NH H 1 and 4 and contains in the positions 6 and 7 at least 0 one halogen atom selected from the group consisting of chlorine and bromine atoms, the other positions of the anthraquinone nucleus being unsubstituted, Aryl stands EXAMPLE 5 for a phenylene radical bearing in para-position to SOr-NH-CHr-CH-CHrCHFCHr-CHI 02H! SOr-NH-QHr-(BH- -CHf-CBi-OH -CH;

EXAMPLE 17 1 ,NH a member selected from the group consisting of ,rhydrogemlower alkyl and lower alkoxy, and R stands S0zNH=-.( H2)1 Ha a for a member selected from the group conslstmg of an f NH i V alkylamin'o'radical containing at least 3 carbon atoms, 01 I v H I u g 7 an alkoxyalkylamino radical containing at least 4 carbon atoms, a dialkylamino radical containing at least 3 carbon 01 atoms, a cycloalkylamino radical, a tetrahydronaphthyL F amino radical and the morpholyl radical. l NH cm 2. A disulfonic acid amide of the anthraquinone series which corresponds to the formula EXAMPLE 19 0 NH CH:

sot-N SOz-NH-Ri 0 NH CH: 01

01 G1 I SO -NH-Bi c1 0 NIH-@011:

NH-GCH:

wherein R stands for a member selected from the group consisting of unbranched and branched octyl radicals, EXAMPLE 20 5 cyclohexyl and tetrahydronaphthyl radicals.

I CgHa SOz-NH-CHz-HE-CHs-CHg-CHr-CH:

0 NH OH:

8 3. The disulfonic acid amide of the anthraquinone 5. The disulfonic acid amide of the authraquinone series which corresponds to the formula series which corresponds to th'e' forrnula NH CH; SOT-NH NEG-OH; 10

6. The disulfonic acid amide of the anthraquinone series which corresponds to the formula CH1 GHQ-CH] SOg-NH-CHr-CH-CHa-CflrCHz-CH:

4. The disulfonic acid amide of the anthraquinone 7. The disulfonic acid amide of the anthraquinone series which corresponds to the formula 'series which corresponds to the formula SO -NH-(C'Hz)7-CH| O NH- CH: CH: CH: O NH OH:

C] SOr-NH-C-CHz- -CH1 C1 HI CH:

sor-Nu-(cmn-om 0 NE on. on. an.

NIH -oH,

SOr-NH--CHr-C-CHI References Citedin the file of this patent UNITED STATES PATENTS 2,731,476 Peter et a1. Jan. 17, 1956 

1. A DISULFONIC ACID AMIDE OF THE ANTHRAQUINONE SERIES WHICH CORRESPONDS TO THE FORMULA 